Polyazo-dyestuffs



POLYAZO-DYESTUFFS Richard- Huss, Arthur Siebert, and Josef Weissert,Frank- 'furt am Main, Germany, assignors to Farbwerke United StatesPatentQ Hoechst Aktiengesellschaft', Frankfurt am Main, Germany, acorporation of Germany No Drawing. Original application May 21, 1954,Serial No. 431,595, now Patent No. 2,777,838, dated January 15, 1957.Divided and this application November 20, 1956, Serial No. 623,300

6 Claims. (Cl. 260-144) The present invention'relates to newpolyazo-dyestufis; more particularly it relates to thepoly'azo-dyestufis corresponding to the following general formula HlN011 Z N=N or the group --N==N'-R R and R 'represent aromatic radicals, Xstands for the diphenyl bond, CH=CH, -NHCONH-, 'CO, O, -S,' -NH or-CONH, Y represents hydrogen or the sulfonic 'acid group, and whereinthe phenyl'radicals a may contain substituents. I V

This application is a division of our mpending-application Serial No.431,595, filed May 21', 1954, now Patent No. 2,777,838 issued January15, 1957. p

r We have found that' new, valuable polyazo-dyestutis corresponding tothe general'constitution acid alkaline (amine 1-amino8-hydroxyor znaphthalene-mem 1 disulfonie acid (amine 3.3-dil1ydroxydi- 4- HgNphenylamine are obtained by coupling 1 molecular proportion of atetra'zo-compound of a diamine of the general-formula "bining thediazo-azo-compound' so obtained in an alkaline or acetic acid mediumwith 1 molecular proportion of a 3.3dihydroxy-diphenylamine and, ifdesired, coupling the resulting polyazo-dyestufi with any 'diazoordiazoazo-compound.

The invention also includes an alternative process for makingpolyazo-dyestuifs f the above constitution,

wherein Z represents hydrogen, the sulfonic acid groupWheren"1-molecular proportion of the tetra'z'otized di- 2,871,230Patented Jan. 2 7, 1959 ice amino compound is coupled in an alkalinemedium with 1 molecular proportion of a1-amino-8-hydroxynaphthalene-rnonoor disulfonic acid or of a1-amino-8-hydroxynaphthalene-monoor disulfoni-c acid coupled in an acidmedium with a diazo-cfompound and the resulting diazoazo-compound iscombined in an alkaline medium with 1 molecular proportion of theazo-dyestutf obtained from a 'sulfonated diazoor diazo-azo-compound and3.3'-dihydroxy-diphenylamine. l

The invention also includes a further process for making the aforesaidpolyazo-dyestufis, wherein 1 molecular proportion of the tetrazotizeddiamino-compound is coupled in an alkaline medium with 1 molecularproportion of a l-amino-8-hydroXynaphthalene-mono ordisulfonic acid orof a 1arnino-8-hydroXynaphthalene-monoor disulfonic acid coupled in anacid medium with a diazocompound and the diazo-azo-compound so obtainedand 1 molecular proportion of a diazoor diazo-azo-com pound are coupledsimultaneously with 1 molecular proportion of3.3'-dihydroxy-diphenylarnine.

The new dyestufis are readily soluble in water and are resistant toinorganic and organic acids as well as to alkalies and formaldehyde.They have a great afiinity for leather fibres, and dye all kinds ofleather by drum dyeing, brush dyeing or spray dyeing, deep full tintswhich range from violet, dark green through dark blue to black andpossess a good to very good fastness to light.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto; the parts being by weight unlessotherwise stated, and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter:

Example 1 A diazo-suspension prepared in the usual manner from 173 partsof laminobenzene-4-sulfonic acid is coupled in an acid medium with 341parts of l-amio-S-hydroxynaphthalene-3.6-disulfonic acid (monosodiumsalt) and the coupling is completed by neutralizing the excess of theacid with a 2 N-solution of sodium acetate; To the suspension of themono-azo-dyestufl so obtained a tetrazosolution prepared from 184 partsof 4.4-diaminodiphenyl is' added at 0 C.5 C. and coupling is conductedin a weakly alkaline medium by adding 2000 parts by volume of a 2N-solution of sodium hydroxide. After stirring the mixture for 30minutes, the alkaline solution of 201 parts of3.3'-dihydroXy-diphenylamine is added in one portion and thereaction-mixture so obtained is stirred overnight at a pH-value of 10.When the coupling is complete, the solution of the trisazo-dyestuff isacidi tied, heated to 92 C., salted out with a small quantity of sodiumchloride, filtered ofi with suction and dried. The dyestufi obtained asa grey-black powder is very readily soluble in water and resistant toinorganic and organic acids, as Well as to formaldehyde and alkalies.The trisazodyestuff so obtained dyes all kinds of leather deepbluish-black uniform tints having a good covering power and very goodfastness to light. to the following formula It corresponds 'HOsS- so r:

Example 2 is complete, the trisazodyestufi is isolated as described inExample 1. The grey-black powder so obtained dyes various kinds ofleather by drum dyeing, brush dyeing and spray dyeing reddish blue-blacktints having a good fastness to light and resistance to inorganic andorganic acids as well as to alkalies and formaldehyde.

Example 3 The trisazo-dyestuif described in Example 1 and having theconstitution l-aminobenzene-4-sulfonic acid acidl-amino-8-hydroxynaphthalene-3.-disulfonic acid alkaline alkaline3.3'-dihydroxy-diphenylamine is converted into the tetrakisazo-dyestuifby coupling it in an alkaline medium at a pH-value of 10 with 173 partsof l-aminobenzene- 4-sulfonic acid. When the coupling is complete, thedye stuff solution is rendered acid, heated to 92 C., salted out with asmall quantity of sodium chloride, filtered off with suction and dried.The tetrakisazo-dyestutf is obtained in the form of a grey-black powderwhich is very readily soluble in water and has the same good fastnessproperties as the dyestuff described in Example 1. It dyes all kinds ofleather by drum dyeing, brush dyeing and spray dyeing uniform bluishblack tints which have, however, a better covering power and a very goodfastness to light. The dyestufi corresponds to the following formula HzNOH compound is coupled to form the trisazo-dyestufi by adding analkaline solution of 201 parts of 3.3-dihydroxydiphenylamine. .Thecoupling solution is stirred overnight and a tetrakisazo-dyestuflf isthen obtained by simultaneously adding to the trisazo-dyestufi adiazo-suspension prepared from 207 parts of l-amino-4-chlorobenzene-3-sulfonic acidand 200 parts by volume of a 5 N-solution of sodiumhydroxide. The dyestufi is isolated as described in Example 3. Thegrey-black powder so obtained dyes all kinds of leather by variousmethods of dyeing weakly reddish dark-blue tints of very good fastnessto light and covering power. The dyestufi has the same fastnessproperties as the dyestufi described in Example 1.

Example 5 The diazo-suspension prepared from 173 parts of 1-aminobenzene-4-sulfonic acid is coupled in an acid medium with 341 partsof l-amino-S-hydroxynaphthalene- 3.6-disulfonic acid (monosodium salt),as described in Example 1. The tetrazo-solution prepared'from 184 partsof 4..4'-diaminodiphenyl-is then pouredrinto the mixture, and couplingis conducte'd in a weakly alkaline medium by adding 2000 parts by volumeof a 2 N-solution of sodium hydroxide, while cooling with ice to 0 C.5C. After stirring for 30 minutes, the alkaline solution of 100 parts of3.3'-dihydroxy-diphenylamine is added to the diazo-disazo-compound, andthe alkaline reaction mixture is stirred overnight. When the coupling iscomplete, the dyestufli solution is rendered acid, heated to 92 C.,precipitated with a small quantity of sodium chloride, filtered ofi withsuction and dried. The hexakisazo-dyestufi is obtained in the form of agrey-black powder which is readily soluble in Water and has remarkablygood resistance to inorganic and organic acids, alkalies andformaldehyde. It dyes all kinds of leather deep bluish black tintshaving a good covering power and a good fastness to light.

Example 6 A diazo-suspension prepared from 22.3 parts of 1-amino-naphthalene-4-sulfonic acid is coupled in the usual manner in anacid medium with 34.1 parts of l-amino- 8-hydroxy-naphthalene-4.fidisulfonic acid. The monoazocompound so obtained is then combined in aweakly alkaline medium with a tetrazo-solution prepared from 36 parts of4.4'-diamino-diphenylether2.2'-disulfonic acid by adding 25 parts ofsodium carbonate. After stirring for 30 minutes, an alkaline solution of20.1 parts of OH H? H 0 3S S 0 511 Example 4 A diaZo-suspension from 207parts of 1-amino-4-chlorobenzene-3-sulfonic acid is coupled in the usualmanner in an acid medium with 341 parts ofl-amino-S-hydroxynaphthalene-4.6-disulfonic acid (monosodium salt) andthe monoazo-dyestufi so obtained is then coupled in a weakly alkalinemedium with a tetrazo-solution prepared from 184 parts of4.4-diamino-diphenyl, while adding 3.3'-dihydroxy-diphenylamine is addedso that the coupling takes place at a pH-value of 10. When the couplingis complete, the trisazo-dyestutf so obtained is combined in an alkalinemedium with a diazo-suspension prepared from 17.3 parts ofl-aminobenzene-4-sulfonic acid to form the tetrakisazo-dyestufi which isisolated in the usual manner, filtered oil? with suction and dried. Thedyestuff obtained in the form of a grey-black powder has 2000 parts byvolume of a 2 N-solution of sodium hy- 76 the same properties as thedyestufi described in Example 2- and dyes leatherreddish blackttint'sofxvery good fastness to=light.-.

Example 7 A diazcesolution prepared from 253 parts ofl-aminobenzene-2.5-disulfonic acidis. couplediin antacid medium in theusual manner with 341 parts of lamino-8-hydroxynaphthalene-3.6-disulfonic acid. When the coupling iscomplete, a tetrazo-solution prepared from 272 parts I Example 8 Bycoupling 1 molecular" proportion of the diazo' disazo compound"describedzin- Example-r1r and having the following constitution:l-aminoben'zene-4-s'ulfonic acid acid1-amino-8-hydroxynaphthalene-3.fi-disulfonic acid alkaline4-.4-diaminodiphenyl, in an alkaline medium" with- 0.95 molecularproportion of the monoazo-dyestuffobtaincd by coupling inan alkalinemedium diazo'tized- 1=-aminobenzene-4-sulfonic acid with 3';3l'--d'ihyd'roxy-d-iphenylamine, and isolating the coupling product after:stirring it inthe usual manner,. a dyestufobtained which has the samegood fastness-and dyeing properties as the dyestuif described in Example3.

Example 9 The clarified diazo-solution prepared'from 1"7.3 part's of l-amino-2-chloro-4 nitrobenzene is: coupled intane'acid medium with: 34.1parts ofi l-aminoa8 hydroxynaphabalone-3;6-disulfonic acid andthe-product so obtained is then coupled in an alkaline medium: with.the: clarified tetrazo-solution prepared from 1 8-4 parts; of. 4.4*-di.-a-minodiphenyl. After stirring fon 301minutes,, thedi'azodisazo-compound so obtained is. immediately coupled withanazo-compound prepared by. combining. in an alkaline medium 201partsrofi=3:3 '-dihydroxy+diphenylamine with the diazo-solution from34.1 parts of l-amino- 8-hydroxynaphthalene-3.6-disulfonic acid. Theresulting tetrakisazo-dyestufi' is isolated as described in theforegoing examples. It dyes leather greenish dark-blue tints of goodgeneral fastnessproperties and very good fastness to light. I

Example 1.0;

1 molecular proportion of the monoazo-compouud obtained by coupling inan acid medium 1 molecular 6 PIOPOI'tlODs, of diazotized l aminobenzeneel sulfonic'; acid with 1 molecular proportion of1-amino-8-hydroxynaphthalene-3.6-disulfonic acid,,is: combined with 1molecular proportion of tetrazotized 4.4-diamino-diphenyl while addingsuch a quantity of a 2 N-solution of sodium hydroxide to produceapH-va'lue of 82 The cliazodisazo compou'nd so obtainedis: coupled inanalkaline medium with the trisazo-dyestufiwhichis prepared by couplingthe monoazo-dyestufi of the' following constitution:4.4'-diamino-diphenyl acid leamino-8-hydroxynaphthalene-3.6-disulfonicacid. in an alkaline:v medium with diazotized. l,-aminobenzene-4-sulfonic' acid and combiningthe intennediate-compound so obtained with 1molecular proportion of 3'.3"diliydroxy'- diphenylamine. When thecoupling is complete, the alkaline solution of thehexakisazo-dyestufi isrendered acid, heated to 92 C., salted out with a small quantity ofsodium chloride, filtered off with. suction and dried. The dyestufiisobtained in theform of agrey-black powder which is readily soluble inwater and has'a good resistance to inorganic and organic acids, alkaliesand formaldehyde. It dyes all kinds of leather by various methods ofdyeing bluish black tints of good fastness to light. The dyestulfcorresponds to the following formula:

Example 11 As described in Example 10, 0.1 molecular proportion of thedi'azo-disazo-compound of the following constitution:l-aminobenzene-4=sulfonic' acid acid1-amino-8-hydroxynaphthalene-3.6-disulfonic acid Example 12 The samedyestuffi as described in Example 10 is obtained by coupling in. analkaline medium the trisazodyestutf of the following constitution:l-aminobenzene- 4-sulfonic. acid acid 71-amino-8-hydroxynaphthalene-3.G-disulfonic acid alkaline4.4'-.diaminodiphenyl 3.3'-dihydroxy-diphenylamine with thediazo-disazo-compound of the following constitution:1-aminobenzene-4-sulfonic acid 1-amino-8-hydroxynaphthalene-3.6-disulfonic acid acid 4.4'-diaminodiphenyl. Thehexakisazo-dyestufi so obtained corresponds with respect to its fastnessand dyeing properties with the dyestufi described in Example 10.

Example 13 1 molecular proportion of the trisazo-dyestuif of thefollowing constitution: 1amino-2-chlorobenzene-4-sulfonic acid acidl-amino-8-hydroxynaphthalene-3.6-disulfonic acid alkaline4.4'-diaminodiphenyl 3.3-dihydroxy-diphenylamine is coupled in analkaline medium with 1 molecular proportion of the diazo-disazo-compoundof the following con-, stitution: 1-aminobenzene-4-sulfonic acidalkaline l-amino-S-hydroxynaphthalene-3.6-disulfonic acid acid4.4'-diaminodiphenyl and the dyestufi so obtained is isolated in theusual manner. The hexakisazo-dyestulf dyes all kinds of leather by drumdyeing, brush dyeing and spray dyeing deep blue black tints of very goodfastness properties.

Example 14 A hexakisazo-dyestufl is obtained by adding in an alkalinemedium to 1 molecular proportion of the diazodisazo-compound of thefollowing constitution: l-aminobenzene-4-sulfonic acid acidl-amino-8-hydroxynaphthalene-3.6-disulfonic acid alkaline4.4'-diaminodiphenyl, while stirring well, 1 molecular E proportionofthe dia zo-disazo-compound of the follow ing constitution:1-aminobenzene-4-sulfonic acid alkaline 1-amino-8hydroxynaphthalene-3.6-disulfonic acid acid 4.4'-diaminodiphenyl andthen introducing the alkaline 0.1 molecular proportion each of the twodiazo-disazocompounds prepared as described in the foregoing examplesand having the following constitutions:

(a) l-aminobenzene-4-sulfonic acid acid - 1-amino-8hydroxynaphthalene-3,fi-disulfonic acid alkaline 4.4'-diaminodiphenyland (b) 1-amino-4-chlorobenzene-3-sulfonic acid 1amino8-hydroxynaphthalene-4.fi-disulfonic' acid alkaline4.4'-diamino-3.3-dimethyldiphenyl are poured together and, after mixingwell, combined in an alkaline medium with an alkaline solution of 0.1

molecular proportion of 3.3'dihydroxy-diphenylamine to form thehexakisazo-dyestufi. It is isolated in the usual manner and dyes leatherdeep blue-black tints of good fastness properties.

Example 16 The diazo-suspension prepared from 173 parts of 1-aminobenzene-4-sulfonic acid is coupled in an acid medium with 341 partsof l-amino-8-hydroxynaphthalene- 3.6-disulfonic acid. When the couplingis complete, the clarified tetrazo-solution of 184 parts of4.4-diarninodiphenyl is added to the monoazo-compound, and 300 parts ofsodium carbonate are then strewn in. The weakly alkaline reactionmixture is stirred for 30 minutes. The diazo-disazo-compound so obtainedis then immediately combined in an alkaline medium with the amcompoundobtained by coupling in an alkaline medium 201 parts of3.3-dihydroxy-diphenylamine with a diazosuspension prepared from 239parts of l-amino-Z-hydroxynaphthalene-4-sulfonic acid. When the couplingis complete, the tetrakisazo-dyestuli obtained is isolated in the usualmanner. The grey-black powder dyes all kinds of leather by variousmethods of dyeing deep, full dark-blue tints having a good coveringpower and a very good fastness to light. The dyestuflf is resistant toinorganic and organic acids as well as to alkalies and formaldehyde. Itcorresponds to the following formula HO OH HOiS- SOa I i 2371.230 9 10 pExample 17' ME-diaminodiphenylis .mi:e;1,..wh{l;:stirring fwiell, with ia iazo-suspension prepare 'orna ..;,par s o -arriinoof 1-2119!!!'h-jdmxyqap hthaknca'q'dlsm' benzene-4-sulfonic acid. Into this mixturean alkaline fomc acld are congbmed m an alkahne m i the solution of' 201parts of 3.3'-dihydroxy-diphenylamine F P P 9 T Q and 1'00"parts.lay-volume 'of aklflN-solution of sodium amme' when t-he' 691-}? mg itheQ 6911p 1mg hydroxide areintroduc'ed'so thatlthe'couplingtakes placeproduct is combined in an alkaline medium with an alin a Stronglyalkaline medium Whnmthe coupling. is kallne solution of 100 P 9l3v7dlih-ydr-oxyrdlphenylfl complete, the tetrakisazo-dyestufi isisolated in the usual amine to form the tetrakisazo-dyestufi which is1solated manner, filtered. ofiwwifllvsucfioni and dried Thg as describedm lthg' t i m Thc-grey-blqck 10 stuff so obtainedhasthe same.fastncssanddyeingprop- Powder so Q l dyes lathey'da-rk'blue tmtS'hav-mg ertiesas the dyestufdes'cribedin Example 3 and dyes a good cowl-mg powr"glued; fasme'ss properties all kinds ofleather bluish'black tints I Thedyestufi corresponds to the following formulaf I HzN LO p p 4" Eic'ample18 In the following tablev'areagiven anumber of further I Ipolyazo-dyestuffs of thisvinvention which dye leather The alkaline;'solntion f'the?-diaz dis'azo?eompo nd '30 similar tints having thesa'me good fastness properties: which is obtained as=described-inExampleLand has the p r .7 v following cbnstitutio'ri': 1-a11'iinobenzene-4-sulfonic acid j eonstwutjio Tint l-amino-8-h ydi'oxynaphaeilbeiadisfilffinic"dcid l' diagino-diphenyl'Qfi 3i3edil'iydroxydiplienyl alkaline i 2. l-amlnobenzene dark blue. 1

S-hydroxyna'phthalen d 1 I a v 40 g4"ddian111inoidlpheny1ainine 33' i to-1 en amine. 4.4-d1am1nod1phenyl; isstirred for30.minutesgand. then }%l.y e m 'aaine adlusted to PH valueaddmg W acid ---14t4.'--diamino-diphenylamine by volume of a SN-solunon of hydrochloricacid. After v monoazo zgm oundfifitydihydroxy' dipheny1 the addition of60*pa'r't's' ofglacialacetic' acid; a solution 3C1 I v aminel-aminobeiizene-wulionic acid. rendered alkaline Wlth S OdlUIIlhydroxide of 201 parts m b 4 fni d acid. h

I V v V v 4.1-am o enzene: -sulo caci l-aininore dis dark of Ph ?ml -5960 P i 8-hydroxynaphthaleneyiifi-disnlfonic acid blue. 7 acetic acidare-added sirnultaneously-dropby dropin 4.4 diamino-diphen'yl monoazo"110cm aci the course of 2 hours.. Due to the buffer ng act on of poundmudmwdibxp diphenylammw the sodium; acetate which is formed, thecoupling to aminobenzenei sulionitizfhid. 8G form the fi takes l? Y of5. i aminobenze'iie' 1 ammo s hydroxy greenishdark When the coupling iscomplete, the trisazo-dyestufi' 1s naphthalenef-3.6-disulfomc acid 4.4'-blue. coupled in an' allgalineiriediuniwith'a; diazo=suspensionammdlphenyl prepared from 173 parts of 1-aminobenzene-4-sulfonic y o g fflla a m 1 m obenacid to form the tetrakisazo-dyestutf which is isolatedin benzene *f f r a N I 7 the usual manner'by acidifying heafing-to 921C. cool. 6. 1 aminobenz'ene 1 amino llih-lhydroxyreddish dark alka blfilterlng ofi W1th c and y grey naphthalene 3.6 disulionic acid 4.4 di-He black powder so obtained dyesall kinds of-leather by p y g ge a qq-3" \trlzlirircilus mefthids' o5 (dyeing the s'lane 'hdeep'black'tgitsas g g qi g g w 3Q Laminoben;

e yestu esc'ri e in xamp e aving a goo cov- Zenaa 1- -h hth t ermg powerand very good fastnessto-light; Thedye- 7 gilfilm ydmxymp alene 24disummm iiglefifi, a

stuff is resistant to inorganic and 'or'ga'nic' acids as well as 9 I t lEF .3 -3- t dilh dro' "-dl hen lammej 4:4--d mm to alkalies andformaldehyde. Y i a- 0 diphenyl lene-2.4-disulioni "Exarfiple'l9 U I j 5s. Lamina-amino 1 amino 8'- hydroxynaphthalene 3.6 disulfonic blue.

acid 4.4 diamino 3.3 dimethyl di- The diazo-disazo-compound obtainableas described phenyl 3.3 dihydroxy diphenylamine in Example 1 and havingthe constitution: l-aminobenl-ammobenzene-z-5-dlsulfonigcacld.zene-4-sulfomc acid 9. 1- -4-sulfonic acid l-aminogreenish black.

. ,8- -3.6-disulfonieaeid 4.4 -urea 3.3 -dihyacid I V.droxyl-aminobenzenei- I a, w .sulfonic d t aci 1-ammo8-hydroxynaphthalene-3,6-disulfonic.acid 10.1- acid l-aminobluish black.

. 1 I 8- -3.6-disulfonic acid 4-- alkaline a drqx ysulfonic acid;

- benzophenone 0 3.3 dihy- 1 aminobenzene 4- lint wherein R representsan aromatic radical selected from 3. The polyazo-dyestufi correspondingto the following the group consisting of radicals of the benzene andnaphformula on E0 HQN OH HOaS- thalene series, X stands for one of thegroup consisting 4. The polyazo-dyestufi corresponding to the followingof the diphenyl bond, CH=CH, NI-I--CONH-, formula OH OH H N OH I NH S 03H H 0 as- S 0 311 CO, O, S, --NH and CONH-, Y 5. The polyazo-dyestuficorresponding to the following stands for a member of the groupconsisting of hydrogen formula OH OH HzN OH and the sulfonic acid group,n-st ands for one of the num- 6. The polyazo-dyestuif corresponding tothe following bers 1 and 2, and wherein the dyestutf molecule containsformula HEN on Hols N=N N=N-C C N=N 11035- S0311 Y Q NH H0=S sour I atleast two sulfonic acid groups.

2. Polyazo-dyesmfis corresponding to the following general formula.

- on on 11.1w or: n-N=N N=N-C ON=N smH a References Cited in the file ofthis patent wherein R represents an aromatlc radical selected from thegroup consisting of radicals of the benzene and UNITED STATES PATENTSnaphthalene series, and n stands for one of the numbers 1 70 1,841,828 7Lieman et a1. Jan. 19, 1932 and 2. 2,777,838 Huss et a1. Ian. 15, 1957

1. POLYAZO-DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA